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UNIT V
NANOCHEMISTRY
PART-A
1. What are nano particles?
Nanoparticles are particles having size of which ranges from 1-50 nm.

2.What are nano materials?

Nanomaterials are the materials having components with size less than 100 nm at
least in one dimension.

3. Define nano-wires.
Nano-wire is a material having an aspect ratio ie., length to width ratio greater than
20. They are also referred to as quantum wires.

4. What is nano –rod?

Nano- rod is a material having an aspect ratio in the range 1 to 20 with short
dimension of the material being 10-100nm.

5. What are nano clusters?

Nano clusters constitute an intermediate state of matter between molecules and bulk
materials .

6. What are CNTs?

Carbon nanotubes (CNT) are allotropes of carbon with a nanostructure having a
length -to-diameter ratio greater than 1,000,000.

7. Define nanochemistry.
Nanochemistry is defined as the study of manipulation of materials at atomic
molecular and macromolecular scales.

8.Name the various methods of synthesis of nano-material.

 Laser ablation
 Chemical vapour depostion
 Precipitation
 Electro- depostion
 Thermolysis

9. What is CVD?
CVD is Chemical Vapour deposition. It is a process of chemically reacting volatile
compound of a material with other gases, to produce a non-volatile solid that deposits
automatically on a suitably placed substrate.

10. Mention the application of Nano-wires.

 Nano-wires are used for enhancing mechanical properties of composites.
 It is used to prepare active electronic components such as p-n junction and logic gates.

11. What are the characteristics of Nano-rods?

 Nano-rods are two-dimensional materials.
 It also exhibits optical and electrical properties.
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12. What is magic number?

It is the number of atoms in the clusters of critical sizes with higher stability.

13. Mention some uses of CNTs.

It is used in battery technology and in industries as catalyst.
It is used in composites, ICs.
CNTs are used effectively inside the human body for drug delivery.

PART-B

1.Explain the properties of Nano-materials.

(i) Melting points:

They have lower melting points and reduced lattice constants.
(ii) Optical properties:
The change in optical properties is caused by two factors.
(a) The quantum confinement of electrons within the nano-particles increases the energy
level spacing.
(b) Surface plasma resonance, which is smaller in size for nano-particles than the
wavelength of incident radiation.
(iii) Magnetic properties:
Bulk materials have ferro-magnetic properties. When the particle size is reduced ,they
get super –paramagnetic properties.
(iv) Mechanical properties:
Mechanical properties of polymeric materials can be increased by the addition of nano-
fillers.
Nano-materials are stronger, harder and more wear resistant and corrosion resistant.
(v) Electrical properties:
(a) Electrical conductivity decreased in reduced dimension.
(b) Electrical conductivity increased in micro-structure.
(vi) Chemical properties:
 In heat treatment of nano material, diffusion of impurities, structural defects, and
dislocation increased.
 Increased perfection will have increased chemical properties.

2. Discuss the laser ablation ,CVD and electrodeposition techniques for the synthesis of
nano-particles.
Top Down / Physical / Hard Methods:
1. Laser Ablation:
Laser Ablation chamber :
High-power laser pulse is used to evaporate the matter from the target .The
total mass ablated from the target per laser pulse is referred to as the ablation rate.
Reaction setup:
When a beam of laser is allowed to irradiate the target, a supersonic jet of
particle is evaporated from the target surface. Simultaneously, an inert gas like
Argon, Helium is allowed into the reactor to sweep the evaporated particles from the
furnace zone to the colder collector.
The ablated species condense on the substrate placed opposite to the target.
The ablation process takes place in a vacuum chamber, or in the presence of some
background gas.
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2.Chemical Vapour Deposition (CVD):

In this process volatile compound of a material chemically react with other gases, to
produce a non-volatile solid that deposit on a substrate.
CVD reaction requires activation energy to proceed .This energy can be provided by
several methods.
a) Thermal CVD:
The reaction is activated by high temperature above 900o C .
b) Plasma CVD:
The reaction is activated by plasma at temperature between 300-700oC.
(c) Laser CVD:
Pyrolysis occurs when laser thermal energy falls on an absorbing substrate.
(d) Photo-laser CVD:
The chemical reaction is induced by UV radiation, which has sufficient photon
energy, to break the chemical bond in the reactant molecules.
Various steps involved in synthesis of CVD are:
1. Transport of gaseous reactant to the surface.
2. Adsorption of gaseous reactant on the surface.
3. Catalysed reaction occurs on the surface.
4. Product diffuses to the growth site.
5. Nucleation and growth occurs on the growth site.
6. Desorption of reaction products away from the surface.
CVD Reactor:
The CVD reactors are of two types
* Hot-wall CVD
* Cold-wall CVD
Hot wall CVD reactors are usually tubular in form and heating is accomplished by
surrounding the reactor with resistance elements.
In cold- wall CVD reactors, substrates are directly heated inductively by graphite
subsectors, while chamber walls are air or water cooled.
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3.ELECTRODEPOSITION:
Template assisted electro deposition is an important technique for synthesizing
metallic nanomaterials with controlled shape and size. Arrays of nano-structured materials
with, specific arrangements can be prepared by this method, using an active template cathode
in an electrochemical cell. The electrodeposition method consists of an electrochemical cell.
The cell usually contains a reference electrode, a specially designed cathodes and an anode.
The cathode substrate on which elelctrodeposition of the nanostructures, can be made of
either non metallic or metallic materials. By using the surface of the cathode as a template,
various desired nanostructures can be synthesized for specific applications.

3.Describe the synthesis of nanomaterials by precipitation and thermolysis method.

Bottom - up methods /Chemical /soft methods:

It involves building up of nano materials from the bottom by atom by atom (=0.1 nm)
or molecule by molecule or cluster by cluster. This method is carried out by the following
process:
1. Precipitation
2. Thermolysis
a) Solvothermal synthesis
b) Hydrothermal synthesis
1. Precipitation method :
Generally nano particles are synthesized by the precipitation reaction between the
reactants in presence of water soluble inorganic stabilizing agent.
Precipitation of BaSO4 Nano particles:
10 g of Sodium hexa meta phosphate (stabilizing agent) was dissolved in 80 ml of
distilled water in 250ml beaker with constant stirring. Then 10ml of 1M sodium sulphate
solution was added followed by 10ml of 1M Barium Nitrate ( Ba (NO3)2 )solution .The
resulting solution was stirred for 1 hour. The resulting precipitate was then centrifuged,
washed with distilled water and vacuum dried.

Ba(NO3)2 + Na2SO4 BaSO4 ↓+ 2NaNO3

In the absence of stabilizing agent, Bulk BaSO4 is obtained.
Precipitation by reduction :
Reduction of metal salt to the corresponding metal atoms .These atoms act as
nucleation centres leading to formation of atomic clusters. These clusters are surrounded by
stabilizing molecule that prevents the atoms agglomerating.
2. Thermolysis method:
Thermolysis is characterized by subjecting the metal precursors (usually
organometallic compounds in oxidation state zero) at high temperatures together with a
stabilising agent. Nano particles show an increase in size relating to the temperature size.
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This is due to the elimination of stabilizing molecule, generating a greater aggregation of the
particles.

Hydrothermal synthesis

a.Hydrothermal synthesis:
It involves crystallization of substances from high temperature aqueous solutions at
high vapour pressure. Hydrothermal synthesis is usually performed below the super critical
temperature of water.(3740).
Method:
Hydrothermal synthesis is performed in an apparatus consisting of a steel pressure vessel
called autoclave in which a nutrient is supplied along with water. A gradient of temperature is
maintained at the opposite ends of the growth chamber, so that the hotter end dissolves the
nutrient and the cooler end cause seeds to take additional growth.

b. Solvothermal synthesis :
Solvothermal synthesis involves the use of solvent under high temperature (between
100o – 1000oc) and moderate to high pressure (1 atm to 10,000 atm ) that facilitate the
interaction of precursors during synthesis.
Method:
A solvent is mixed with certain metal precursors and the solution mixture is placed in
an autoclave kept at relatively high temperature and pressure in an oven to carry out the
crystal growth. The pressure generated in the vessel, due to the solvent vapour , elevates the
boiling point of the solvent.
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Eg: Methanol, Ethanol, Toluene, Cyclohexane ,etc.

Solvothermal synthesis of Zinc oxide:
Zinc acetate dehydrate is dissolved in 2-propanol at 50oC. Subsequently the solution
is cooled to 0oC and NaOH is added to form ZnO. The solution is then heated to 65oC to
allow ZnO growth for some period of time before a capping agent (1-dodecanethiol) is
injected to the suspension to arrest growth. The rod shaped ZnO nano-crystal is obtained.
Uses:
→ Much geometry including thin film, bulk powder, and single crystals can be prepared.
→ Thermodynamically stable novel materials can also be prepared easily.

4. Write a short note on Nano wires, Nano rods and Nano clusters.
Nano –wires:
Nano-wire is a material having an aspect ratio i.e. length to width ratio greater than
20. Nano –wires are also referred to as “quantum wires”.
 Nano –Wires of metals: Au ,N i,Pt
 Nano –Wires of semiconductors: Si, GaN
 Nano –Wires of Insulators: SiO2, TiO2
 Molecular Nano –Wires: DNA
Characteristics of Nano- Wires :
> Nano- Wires are one – dimensional material.
> Conductivity of a nano-wire is less than that of the corresponding bulk materials.
> It exhibits distinct optical, chemical, thermal and electrical properties due to this
large surface area.
> Silicon nano-wires show strong photoluminescence characteristics.
Synthesis of nanowires:
1. Template assisted synthesis:
The templates contain very small cylindrical pores or voids within the host material
and the empty spaces are filled with the chosen material to form nanowires.
Eg. Mesoporous Alumina
2.VLS method:
This method is used for the production of single crystal of semiconductors of
elemental Silicon and Germanium. The mechanism involves a gas phase reaction followed by
anisotropic crystal growth (different properties in different directions). For example the laser
ablation and thermal evaporation of a solid target made of pure Si powder mixed with metals
(Fe, Co, Ni) catalyst at 1200o -1400o C followed by condensation on a substrate maintained at
900o-1100o C facilitates the growth of long Si nanowires with diameters in the range of 20-80
nm. Each wire consists of crystalline Si core encased by an outer layer of silicon dioxide.
Applications of nanowires:
 Nanowires are used to enhance mechanical properties of composites.
 Semiconductor nanowires are used as components in making transistors, diodes, logic
gates and digital computing.
 Nanowires find applications in high density data storage either as magnetic read
heads.

Nano Rods:
Nano rods are a material having an aspect ratio in the range 1 to 20 nm.
Characteristics of Nano rods:
 It exhibits special optical and electrical properties.
 Nano rods are two dimensional materials.
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Synthesis of Nano rods:

Direct chemical synthesis:
Metal atoms are combined with ligands which act as shape control agents which make
bonds with different metal atoms of different strength to get nano rods.
Applications of nanorods:
Nano rods are used in display technology and micromechanical switches.

Nano clusters:
Nano clusters are multi atom particles of size intermediate between molecule and bulk
materials. The size of nano clusters range from 1-10nm .The atoms or molecules in a clusters
are bound by any of the forces like covalent, ionic, Vander waal’s forces. When a gas
condenses in to cluster of atoms the no. of atoms in these clusters varies between a few to
hundreds. Clusters of certain size called critical size are more stable than others (200-103
atoms).

The no. of atoms in a cluster of critical size with higher stability is called Magic
number. Cluster of transition metal atoms have chemical, electronic, magnetic properties
which vary with number of constituent atoms.
Source of clusters:
Super sonic nozzle source:
The metal is vaporized in an oven and mixed with inert carrier gas at a pressure of
several atmospheres at a temperature of 75-1500K .Metal/ Carrier gas mixture is allowed to
pass through the nozzle in to high vacuum which produces a supersonic beam of the mixture.
The carrier gas produces large clusters. In the absence of carrier gas small clusters are
produced.
Gas aggregation source:
Vapours of metal atoms are introduced in to inert gas which is maintained at high
pressure and high temperature. The gas phase is supersaturated with metallic species and
aggregates. It acts as a seed and produces a continuous beam of nano clusters.
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5. Discuss the application of Nano materials in various fields.

Applications of Nano materials:
 Industries
1. As catalyst:
The nano materials have more no. of surface atoms which make them catalytically
active. For example, bulk gold chemically inert white nano gold possess excellent catalytic
property.
2. Water purification:
Dissolved salts and colour producing organic compounds can be filtered very easily
from water by using nano porous membrane having pores smaller than 10nm.Magnetic nano
particles are used to remove heavy metal contamination from waste water.
3. In Fabric industry:
Embedding of Nano particles on fabrics make them stain repellent. Socks embedded
with silver nano particles remove the bacteria and makes them odour free.
4. In automobiles:
Fuel consumption in automobiles can be reduced by using specially designed nano
particles as fuel additives. Incorporation of small amount of nano particles in car
bumpers make them stronger than steel
5. In food industry:
Nano particles are used to make packing material and containers to store food.
6. In Solar cells:
Absorption of solar radiation in solar cells containing nano particles are higher than
the bulk materials.
 Medicine :
1. Nano drugs:
Nano materials are used as drugs for the treatment of cancer and TB.
2. Nano medibots :
Nano particles act as nano medibots which identify and penetrate the cancer cells
and destroy them by supplying anti cancer drugs
3. Gold coated Nano shells:
Gold coated nano shells containing silicon core are administered near the tumours .
When IR light is irradiated on the skin externally, the gold nano shells absorb the light
and convert in to heat which destroys the cancer cells responsible for tumour.
4. Gold nano particles as sensors:
Nano gold when mixed with different type microorganisms show different colours
which is used to identify the harmless and dangerous micro organisms.
5. Protein analysis:
Gold nano particles injected in to the body reacts with the protein and the protein
concentration can be detected by passing laser beam externally.
6. Gold nano shells for blood Immune assay:
Gold nano shells are used to detect WBC count in blood.
7. Gold nano shells in Imaging:
Gold nano shells is used as a scanning probe which gives the magnified image of
cells in a body
8. Targetted drug delivery:
It involves slow and selective release of drug to the targeted organs.
 Electronics:
1. Quantum wires have electrical conductivity
2. Nano radios are produced by using CNT
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3. MOSFET (Metal Oxide Semiconductor Field Effect Transistor) is used for

Amplifying and switching electronic signals.
4. Nano wires are used to build transistors without p-n junction diode.
5. Transistor called NOMFET (Nano particle Organic Memory Field effect
transistor) is created by combining Gold nano particles with organic molecules
 Biomaterials:
1. Nano materials are used as bone cement and bone plates in hospitals
2. It is used as material for joint replacement
3. It is used in the manufacture of some components like heart valves, contact
lenses, dental implants etc.

6. Write a short note on CNT.

Carbon NanoTubes ( CNTs) :
CNTs are allotropes of carbon in the form of molecular scale tubes made of graphitic
carbon with unique mechanical and electrical / electronic properties with potential
applications in electronic, information technology and medical fields.
Carbon nanotubes were discovered by Sumio Iijima 1991, while preparing C60
molecules by the carbon arc process. They are also known as tubular fullerenes and are
cylindrical graphene sheets of sp2 bonded carbon atoms.
These nanotubes are single molecules measuring few nanometers in diameter and several
microns in length. Depending on the growth process, the length of the tubes can be 100
nanometers to several microns (1 micron = 1000 nm), the diameter varying from 1 to 20
nanometers

Structure of CNTs:
Carbon nanotube is a tabular form of carbon with 1-3 nm diameters and a length of few nm
to microns. Each carbon atom in the carbon nanotubes is linked by the covalent bond. They
are two types of nanotubes.
1. Single walled carbon nanotubes (SWCNT) having a diameter of 1 nm. Three types of
SWCNTs are as follows:
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2. Multi-walled nanotubes (MWNTs) or nested nanotubes consist of multiple layers of

graphite rolled to form tube shape.

MutliwalledNanotube
Synthesis of Carbon Nano Tubes:
Carbon nanotubes are prepared by the following methods.
 Pyrolysis of hydrocarbons.
 Laser evaporation
 Carbon arc method.
 Chemical vapour decomposition.
Pyrolysis of Hydrocarbon:
Carbon nano tubes are synthesized by the pyrolysis of hydrocarbons such as acetylene
at about 700oC in the presence of Fe-Silica or Fe-graphite catalyst under inert conditions.
Laser Evaporation:
It involves vapourization of graphite target, containing small amount of cobalt
and nickel, by exposing it to an intense pulsed laser beam at higher temperature (1200oC) in a
quartz tube reactor. An inert gas such as argon is simultaneously allowed to pass into the
reactor to sweep the evaporated carbon atoms from the furnace to the colder collector, on
which they condense as carbon nanotubes.
Carbon arc Method:
It is carried out by applying direct current (60-100 A and 20 – 25 V) arc between
graphite electrodes of 10-20 µm diameters. The discharge vapourizes one of the carbon rods
and forms a small rod- shaped deposit on the other rod. The yield depends on the uniformity
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of the plasma arc and the temperature. The deposits contain 10 – 50 SWNTs, the average
size about 1.4 nm in diameter and about 10 µm in length.
Chemical Vapour Deposition:
It involves decomposition of vapour of hydrocarbons such as methane, acetylene,
ethylene, etc., at high temperatures (1100oC) in presence of metal nanoparticle catalyst like
nickel, cobalt, iron supported on MgO or Al2O3. Carbon atoms produced by the
decomposition condense on a cooler surface of the catalyst.

Properties of CNTs:
(1) Mechanical Properties:
Young’s modulus of carbon nano tubes is 10 times greater than that of steel. CNTs
have very structural defects in their walls, and hence, do not fracture on bending. The tensile
strength of CNTs is about about 20 times that of steel.
(2) Electrical Properties:
The electrical properties of CNTs vary between metallic to semiconducting materials.
The very high electrical conductivity of CNT is due to the minimum defects in the structure.
(3) Thermal Conductivity:
The thermal conductivity of CNT is very high due to the vibration of covalent bonds
due to minimum defects in the structure.

Applications of Carbon NanoTubes:

Due to the unusual and unique properties of CNTs they find potential applications in
the following field:

 Carbon nanotubes play an important role in the battery technology, because some
charge carriers can be successfully stored inside the nanotubes.
 Multi-walled CNTs can be used as storage devices to store hydrogen gas in fuel cells.
 CNTs are used as catalyst in chemical reactions.
 CNTs can be used for drug delivery within the body by placing the drugs within the
tubes or by attaching the drug to the sides of the tubes.
 CNTs are used as light weight shielding materials to protect electronic equipments
from electromagnetic radiation.